Method of increasing retention in papermaking using colloidal borosilicates

ABSTRACT

The invention comprises a borosilicate retention aid composition and a method for improving the production of paper by addition of the borosilicate. The borosilicate may be utilized in conjunction with a high molecular weight synthetic flocculant and/or starch, with or without the addition of a cationic coagulant. The borosilicate material is preferably a colloidal borosilicate. Methods for the preparation of the borosilicate material are disclosed.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The invention relates to a borosilicate retention aid compositionand, a method of using the borosilicate retention aid composition in theproduction of paper. A method of making such borosilicate retention aidcomposition is also disclosed. The borosilicate materials are preferablyan aqueous suspension of colloidal borosilicate.

[0003] 2. Background of the Invention

[0004] In the manufacture of paper, an aqueous cellulosic suspension orfurnish is formed into a paper sheet. The slurry of cellulosic fiber isgenerally diluted to a consistency (percent dry weight of solids in thefurnish) having a fiber content of about 4 weight percent of fiber orless, and generally around 1.5% or less, and often below 1.0% ahead ofthe paper machine, while the finished sheet typically has less than 6weight percent water. Hence the dewatering and retention aspects ofpapermaking are extremely important to the efficiency and cost of themanufacture.

[0005] Gravity dewatering is the preferred method of drainage because ofits relatively low cost. After gravity drainage more expensive methodsare used for dewatering, for instance vacuum, pressing, felt blanketblotting and pressing, evaporation and the like. In actual practice acombination of such methods is employed to dewater, or dry, the sheet tothe desired water content. Since gravity drainage is both the firstdewatering method employed and the least expensive, an improvement inthe efficiency of this drainage process will decrease the amount ofwater required to be removed by other methods and hence improve theoverall efficiency of dewatering and reduce the cost thereof.

[0006] Another aspect of papermaking that is extremely important to theefficiency and cost is retention of furnish components on and within thefiber mat. The papermaking furnish represents a system containingsignificant amounts of small particles stabilized by colloidal forces. Apapermaking furnish generally contains, in addition to cellulosicfibers, particles ranging in size from about 5 to about 1000 nmconsisting of for example cellulosic fines, mineral fillers (employed toincrease opacity, brightness and other paper characteristics) and othersmall particles that generally, without the inclusion of one or moreretention aids, would in significant portion pass through the spaces(pores) between the mat formed by the cellulosic fibers on thepapermachine.

[0007] Greater retention of fines, fillers, and other components of thefurnish permits, for a given grade of paper, a reduction in thecellulosic fiber content of such paper. As pulps of lower quality areemployed to reduce papermaking costs, the retention aspect ofpapermaking becomes more important because the fines content of suchlower quality pulps is generally greater. Greater retention alsodecreases the amount of such substances lost to the whitewater and hencereduces the amount of material wastes, the cost of waste disposal andthe adverse environmental effects therefrom. It is generally desirableto reduce the amount of material employed in a papermaking process for agiven purpose, without diminishing the result sought. Such add-onreductions may realize both a material cost savings and handling andprocessing benefits.

[0008] Another important characteristic of a given papermaking processis the formation of the paper sheet produced. Formation may bedetermined by the variance in light transmission within a paper sheet,and a high variance is indicative of poor formation. As retentionincreases to a high level, for instance a retention level of 80 or 90%,the formation parameter generally declines.

[0009] Various chemical additives have been utilized in an attempt toincrease the rate at which water drains from the formed sheet, and toincrease the amount of fines and filler retained on the sheet. The useof high molecular weight water soluble polymers was a significantimprovement in the manufacture of paper. These high molecular weightpolymers act as flocculants, forming large flocs which deposit on thesheet. They also aid in the dewatering of the sheet. In order to beeffective, conventional single and dual polymer retention and drainageprograms require incorporation of a higher molecular weight component aspart of the program. In these conventional programs, the high molecularweight component is added after a high shear point in the stock flowsystem leading up to the headbox of the paper machine. This is necessarysince flocs are formed primarily by the bridging mechanism and theirbreakdown is largely irreversible and do not re-form to any significantextent. For this reason, most of the retention and drainage performanceof a flocculant is lost by feeding it before a high shear point. Totheir detriment, feeding high molecular weight polymers after the highshear point often leads to formation problems. The feed requirements ofthe high molecular weight polymers and copolymers which provide improvedretention often lead to a compromise between retention and formation.

[0010] While successful, high molecular weight flocculant programs wereimproved by the addition of so called inorganic “microparticles”.

[0011] Polymer/microparticle programs have gained commercial successreplacing the use of polymer-only retention and drainage programs inmany mills. Microparticle containing programs are defined not only bythe use of a microparticle component but also often by the additionpoints of chemicals in relation to shear. In most microparticlecontaining retention programs, high molecular weight polymers are addedeither before or after at least one high shear point. The inorganicmicroparticulate material is then usually added to the furnish after thestock has been flocculated with the high molecular weight component andsheared to break down those flocs. The microparticle additionre-flocculates the furnish, resulting in retention and drainage that isat least as good as that attained using the high molecular weightcomponent in the conventional way (after shear), with no deleteriousimpact on formation.

[0012] One such program employed to provide an improved combination ofretention and dewatering is described in U.S. Pat. Nos. 4,753,710 and4,913,775, to Langley et al., the disclosures of which are hereinafterincorporated by reference into this specification. In the methoddisclosed in Langley et al., a high molecular weight linear cationicpolymer is added to the aqueous cellulosic papermaking suspension beforeshear is applied to the suspension, followed by the addition ofbentonite after the shear application. Shearing is generally provided byone or more of the cleaning, mixing and pumping stages of thepapermaking process, and the shear breaks down the large flocs formed bythe high molecular weight polymer into microflocs. Further agglomerationthen ensues with the addition of the bentonite clay particles.

[0013] Other such microparticle programs are based on the use ofcolloidal silica as a microparticle in combination with cationic starchsuch as that described in U.S. Pat. Nos. 4,388,150 and 4,385,961, thedisclosures of which are hereinafter incorporated by reference into thisspecification, or the use of a cationic starch, flocculant, and silicasol combination such as that described in both U.S. Pat. Nos. 5,098,520and 5,185,062, the disclosures of which are also hereinafterincorporated by reference into this specification. U.S. Pat. No.4,643,801 claims a method for the preparation of paper using a highmolecular weight anionic water soluble polymer, a dispersed silica, anda cationic starch.

[0014] Although, as described above, the microparticle is typicallyadded to the furnish after the flocculant and after at least one shearzone, the microparticle effect can also be observed if the microparticleis added before the flocculant and the shear zone (e.g., wherein themicroparticle is added before the screen and the flocculant after theshear zone).

[0015] In a single polymer/microparticle retention and drainage aidprogram, a flocculant, typically a cationic polymer, is the only polymermaterial added along with the microparticle. Another method of improvingthe flocculation of cellulosic fines, mineral fillers and other furnishcomponents on the fiber mat using a microparticle is in combination witha dual polymer program which uses, in addition to the microparticle, acoagulant and flocculant system. In such a system a coagulant is firstadded, for instance a low molecular weight synthetic cationic polymer orcationic starch. The coagulant may also be an inorganic coagulant suchas alum or polyaluminum chlorides. This addition can take place at oneor several points within the furnish make up system, including but notlimited to the thick stock, white water system, or thin stock of amachine. This coagulant generally reduces the negative surface chargespresent on the particles in the furnish, particularly cellulosic finesand mineral fillers, and thereby accomplishes a degree of agglomerationof such particles. The coagulant treatment is followed by the additionof a flocculant. Such a flocculant generally is a high molecular weightsynthetic polymer which bridges the particles and/or agglomerates, fromone surface to another, binding the particles into larger agglomerates.The presence of such large agglomerates in the furnish, as the fiber matof the paper sheet is being formed, increases retention. Theagglomerates are filtered out of the water onto the fiber web, whereasunagglomerated particles would, to a great extent, pass through such apaper web. In such a program the order of addition of the microparticleand flocculant can be reversed successfully.

[0016] The present invention departs from the disclosures of thesepatents in that a borosilicate, preferably a colloidal borosilicate isutilized as the microparticle. Surprisingly we have found thatborosilicates provide improved performance over other microparticleprograms, and especially those using colloidal silica sols as themicroparticle. The borosilicate microparticles of the invention allowthe production of paper and board having improved levels of retention,formation, uniform porosity, and overall dewatering.

SUMMARY OF THE INVENTION

[0017] One aspect of the invention comprises a borosilicate retentionaid composition. The borosilicates, preferably aqueous solutions ofcolloidal particles of borosilicate, useful in this invention have amole ratio of boron to silicon of from 1:1000 to 100:1 and generallyfrom 1:100 to 2:5. Preferably the mole ratio of sodium to silicon in theborosilicate materials of this invention ranges from 0.006 to 1.04 andeven more preferably ranges between 0.01 to 0.7. A further aspect of theinvention comprises a papermaking system which comprises the steps ofadding to a papermaking furnish from about 0.00005 to about 1.25% byweight, based on the weight of the dry fiber in the furnish, of aborosilicate. In an alternative embodiment, a nonionic, cationic, oranionic polymeric flocculant is added to the furnish either before orafter addition of the borosilicate in an amount of from about 0.001 toabout 0.50% by weight based on the dry weight of fiber in the furnish.An alternative is the addition of cationic starch or guar gum in placeof or in addition to a polymeric flocculant to the furnish either beforeor after addition of the borosilicate in an amount of from about 0.005to about 5.0% by weight based on the dry weight of fiber in the furnish.Another alternative is the addition of a coagulant to the furnish in anamount ranging from 0.005 to 1.25% by weight of the dry weight of thefiber in the furnish. The flocculation of components of the papermakingfurnish is increased when the borosilicate is added alone or incombination with a conventional polymeric flocculant, alone or incombination with a coagulant.

[0018] By the addition of the borosilicate particles of this inventionto a papermaking furnish or slurry prior to sheet formation, improvedsheet properties may be obtained. As used herein, the term furnish orslurry is meant as a suspension of cellulosic fibers used to form acellulosic sheet. The sheet may be a fine paper (which as used hereinincludes virgin-fiber- based as well as recycle-fiber based materials),board (which as used herein includes recycle-fiber based test liner andcorrugating medium as well as virgin-fiber based materials), andnewsprint (which as used herein includes magazine furnishes as well asboth virgin fiber and recycle-fiber based), or other cellulosicmaterial. The final sheet may contain in addition to a cellulosic fibermat, fillers, pigments, brighteners, sizing agents, and other materialsused in the production of the numerous grades of cellulosic matscommonly referred to as paper or board.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The invention comprises a retention and drainage aid compositioncomprising a borosilicate (preferably a colloidal borosilicate) having amole ratio of boron to silicon ranging from about 1:100 to about 2:5. Ina preferred embodiment of the invention, the borosilicate ischaracterized as having a mole ratio of sodium to silicon ranging fromabout 6:1000 to 1.04:1. The microparticle retention aid is preferably acolloid of borosilicate having a chemistry similar to that ofborosilicate glass. The borosilicate is preferably used in the form ofan aqueous colloid. This colloid is generally prepared by reacting analkali metal salt of a boron containing compound with silicic acid underconditions resulting in the formation of a colloid. The borosilicateparticles useful in this invention may have a particle size over a widerange, for example from 1 nm (nanometer) to 2 microns (2000 nm), andpreferably from 1 nm to 1 micron. When a colloidal borosilicate isutilized the particle size will generally be in the range of from 1 nmto 200 nm and preferably from 1 to 80 nm, and most preferably 20-80 nm.The surface area of the borosilicate particles useful in this inventioncan likewise vary over a wide range. Generally as particle sizedecreases, surface area will increase. The surface area should be in therange of 15 to 3000 m²/g and preferably 50 to 3000 m²/g. When thepreferred colloidal borosilicate particles of the invention are utilizedthe surface area will generally be in the range of 250 to 3000 m²/g andpreferably from 700 to 3000 m²/g.

[0020] The preferred colloidal borosilicate materials useful in thisinvention are generally prepared by first preparing silicic acid. Thismay be advantageously accomplished by contacting an alkali metalsilicate solution, preferably a dilute solution of the alkali metalsilicate with a commercial cation exchange resin, preferably a so calledstrong acid resin, in the hydrogen form and recovering a dilute solutionof silicic acid. The silicic acid may then be added, with agitation to adilute solution of an alkali metal borate at a pH of from 6-14, and acolloidal borosilicate product suspended in water is recovered.Alternatively, the alkali metal borate and the silicic acid may be addedsimultaneously to prepare suitable materials. In the usual practice ofthis invention, the concentration of the silicic acid solution utilizedis generally from 3 to 8 percent by weight SiO₂, and preferably 5 to 7percent by weight SiO₂. The weight percent of the borate solutionutilized is generally 0.01 to 30 and preferably 0.4 to 20 weight percentas B₂O₃. The borate salt utilized may range over a wide variety ofcompounds. Commercial borax, sodium tetraborate decahydrate, or sodiumtetraborate pentahydrate are the preferred material in the practice ofthis invention because of the ready availability of these materials andtheir low cost. Other water soluble borate materials may be utilized. Webelieve that any soluble alkali metal borate salt may be employed in thepractice of this invention. The preparation of the colloidalborosilicate material of this invention may be accomplished with orwithout pH adjustment. It is sometimes advisable to conduct the reactionat a pH of 7.5 to 10.5 through the addition of an appropriate alkalimetal hydroxide, preferably sodium hydroxide, to the reaction mixture.Best results have been obtained in the pH range of 8 to 9.5 although aswill be appreciated, the synthesis procedures for the borosilicatecompositions of this invention are still being optimized. We believethat agitation, rate of addition, and other parameters are non-criticalto the formation of the colloidal borosilicate compositions of theinvention. Other methods of preparing the colloidal borosilicates ofthis invention may also be utilized. These methods could encompasspreparing the colloidal borosilicate as above and spray drying theparticles followed by grinding, or other methods which would yield aborosilicate material meeting the parameters set forth above.

[0021] The invention further comprises a method of improving theproduction of paper which comprises the step of adding to a paper millfurnish from about 0.00005 to about 1.25% by weight based on the dryweight of fiber in the slurry or furnish of a borosilicate, preferably acolloidal borosilicate. In an alternative embodiment, a nonionic,cationic or anionic polymeric flocculant may be added to the furnisheither before or after the addition of the borosilicate in an amount offrom about 0.001 to about 0.5% by weight based on dry weight of fiber inthe furnish. A cationic starch may alternatively be added to the furnishin place of, or in addition to the synthetic polymer flocculant in anamount of from about 0.005 to about 5.0% by weight based on the dryweight of fiber in the furnish. More preferably, the starch is added inan amount of from about 0.05 to about 1.5% by weight based on the dryweight of fiber in the furnish. In yet another embodiment, a coagulantmay be added to the furnish in place of, or in addition to, theflocculant and/or the starch in an amount of from about 0.005 to about1.25% by weight based on the dry weight of fiber in the papermakingfurnish. Preferably the coagulant is added in an amount of from about0.025 to about 0.5% by weight based on the dry weight of fiber in thefurnish.

[0022] This invention is also directed to a method for increasingretention and drainage of a papermaking furnish on a papermaking machinewhich comprises the steps of adding to a papermaking furnish from about0.00005 to about 1.25% by weight based on the dry weight of fiber in thefurnish of a borosilicate particle, preferably a colloidal borosilicate.The borosilicate may be added to the papermaking furnish along with anonionic, cationic or anionic polymeric flocculant. The flocculant maybe added either before or after the borosilicate in an amount of fromabout 0.001 to about 0.5% by weight based on the dry weight of fiber inthe furnish. Starch may alternatively be added to the furnish in placeof or in addition to the flocculant in an amount of from about 0.005 toabout 5.0% by weight based on dry weight of fiber in the furnish. Ifstarch is utilized it is preferably a cationic starch. When used, thestarch is preferably added in an amount of from about 0.05 to about 1.5%by weight based on the dry weight of fiber in the furnish. In yetanother alternative, a coagulant may be added to the furnish in placeof, or in addition to, the flocculant and/or the starch in an amount offrom about 0.005 to about 1.25% by weight based on the dry weight offiber in the furnish. Preferably, the coagulant is added in an amount offrom about 0.025 to about 0.5% by weight based on the dry weight offiber in the furnish.

[0023] The dosage of the polymeric flocculant in any of the aboveembodiments is preferably from 0.005 to about 0.2 weight percent basedon the dry weight of fiber in the furnish. The dosage of theborosilicate is preferably from about 0.005 to about 0.25 percent byweight based on the weight of dry fiber in the furnish, and mostpreferably from about 0.005 to about 0.15% by weight of fiber in thefurnish.

[0024] It should be pointed out that since this invention is applicableto a broad range of paper grades and furnishes the percentages givenabove may occasionally vary. It is within the spirit and intent of theinvention that variance can be made from the percentages given abovewithout departing from the invention, and these percentage values aregiven only as guidance to one skilled in the art.

[0025] In any of the above embodiments, bentonite, talc, syntheticclays, hectorite, kaolin, or mixtures thereof may also be added anywherein the papermaking system prior to sheet formation. The preferredaddition point is the thick stock pulp before dilution with whitewater.This application results in increased cleanliness of the papermakingoperation which otherwise experiences hydrophobic deposition affectingboth the productivity and the quality of paper.

[0026] In addition, any of the above embodiments may be applied topapermaking furnish selected from the group consisting of fine paper.(which as used herein includes virgin fiber based as well asrecycle-fiber based materials), board (which as used herein includesrecycle-fiber based test liner and corrugating medium as well asvirgin-fiber based materials), and newsprint (which as used hereinincludes magazine furnishes as well as both virgin fiber andrecycle-fiber based), or other cellulosic material. These furnishesinclude those that are wood-containing, wood-free, virgin, bleachedrecycled, unbleached recycled, and mixtures thereof.

[0027] Paper or paperboard is generally made from a suspension orfurnish of cellulosic material in an aqueous medium, which furnish issubjected to one or more shear stages, in which such stages generallyare a cleaning stage, a mixing stage and a pumping stage, and thereafterthe suspension is drained to form a sheet, which sheet is then dried tothe desired, and generally low, water concentration. The borosilicatematerials of the invention may be added to the furnish before or after ashear stage.

[0028] In addition to the retention and drainage aid applicationsdescribed above, the borosilicate materials may be used in conjunctionwith standard cationic wet strength resins to improve the wet strengthof cellulosic sheet so treated. When utilized in this manner theborosilicate is added to the furnish prior to placement of the furnish,containing the wet strength resin, on a papermachine. The borosilicateis generally utilized at the levels set forth above.

[0029] The borosilicate of this invention has been found tosignificantly enhance the performance of synthetic polymeric flocculantsand retention aids, and starch in the papermaking process. Further, theborosilicate materials are believed to have utility as additives insolids/liquids separation processes such as water pretreatment, and inwastewater treatment applications. The borosilicates in addition toenhancing drainage and retention in newsprint, fine paper, board andother paper grades, may also find utility in pitch and stickies controlin papermaking, pulp dewatering in the production of dry-lap pulp,saveall and clarifier applications in pulp and paper mills, waterclarification, dissolved air flotation and sludge dewatering. Thecompositions of this invention may also find utility in solid/liquidseparation or emulsion breaking. Examples of such applications aremunicipal sludge dewatering, the clarification and dewatering of aqueousmineral slurries, refinery emulsion breaking and the like. The enhancedperformance seen utilizing the borosilicate particles of this inventionin combination with synthetic polymers and or starch includes higherretention, improved drainage and improved solids/liquids separation, andoften a reduction in the amount of polymer or starch used to achieve thedesired effect.

[0030] Microparticle retention programs are based on the restoration ofthe originally formed flocs broken by shear. In such applications, theflocculant is added before at least one high shear point, followed bythe addition of microparticle just before the headbox. Typically, aflocculant will be added before the pressure screens, followed by theaddition of microparticle after the screens. However a method whereinthis order may be reversed is contemplated herein. Secondary flocsformed by the addition of microparticles result in increased retentionand drainage without detrimentally affecting formation of the sheet.This allows increased filler content in the sheet, eliminatestwo-sidedness of the sheet, and increases drainage and speed of themachine in paper manufacturing.

[0031] The use of a slight excess of polymeric flocculant and/orcoagulant is believed necessary to ensure that the subsequent shearingresults in the formation of microflocs which contain or carry sufficientpolymer to render at least parts of their surfaces positively charged,although it is not necessary to render the whole furnish positivelycharged. Thus the zeta potential of the furnish, after the addition ofthe polymer and after the shear stage, may be cationic or anionic.

[0032] Shear may be provided by a device in the apparatus used for otherpurposes, such as a mixing pump, fan pump or centriscreen, or one mayinsert into the apparatus a shear mixer or other shear stage for thepurpose of providing shear, and preferably a high degree of shear,subsequent to the addition of the polymer.

[0033] The flocculants used in the application of this invention arehigh molecular weight water soluble or dispersible polymers which mayhave a cationic or anionic charge. Nonionic high molecular weightpolymers may also be utilized. These polymers may be completely solublein the papermaking system, or alternatively may be readily dispersible.They may have a branched or crosslinked structure provided that they donot form objectionable “fish eyes”, so called globs of undissolvedpolymer on the finished paper. Polymers of these types are readilyavailable from a variety of commercial sources. They are available asdry solids, aqueous solutions, water-in-oil emulsions which when addedto water allow the polymer contained therein to rapidly solubilize, oras dispersions of the water soluble or dispersible polymer in aqueousbrine solutions. The form of the high molecular weight flocculant usedherein is not deemed to be critical so long as the polymer is soluble ordispersible in the furnish.

[0034] As stated above, the polymers may be cationic, anionic, ornonionic. Cationic polymer flocculants useful herein are generally highmolecular vinyl addition polymers which incorporate a cationicfunctional group. These polymers are generally homopolymers of watersoluble cationic vinyl monomers, or may be copolymers of a water solublecationic vinyl monomer with a nonionic monomer such as acrylamide ormethacrylamide. The polymers may contain only one cationic vinylmonomer, or may contain more than one cationic vinyl monomer.Alternatively, certain polymers may be modified or derivatized afterpolymerization such as polyacrylamide by the mannich reaction to producea cationic vinyl polymer useful in the invention. The polymers may havebeen prepared from as little as 1 mole percent cationic monomer to 100mole percent cationic monomer, or from a cationically modifiedfunctional group on a post polymerization modified polymer. Most oftenthe cationic flocculants will have at least 5 mole percent of cationicvinyl monomer or functional group, and most preferably, at least 10weight percent of cationic vinyl monomer or functional group.

[0035] Suitable cationic vinyl monomers useful in making thecationically charged vinyl addition copolymers and homopolymers of thisinvention will be well known to those skilled in the art. Thesematerials include: dimethylaminoethyl methacrylate (DMAEM),dimethylaminoethyl acrylate (DMAEA), diethylaminoethyl acrylate (DEAEA),diethylaminoethyl methacrylate (DEAEM) or their quaternary ammoniumforms made with dimethyl sulfate or methyl chloride, mannich reactionmodified polyacrylamides, diallylcyclohexylamine hydrochloride (DACHAHCl), diallyldimethylammonium chloride (DADMAC),methacrylamidopropyltrimethylammonium chloride (MAPTAC) and allyl amine(ALA). Cationized starch may also be used as a flocculant herein. Theflocculant selected may be a mixture of those stated above, or a mixtureof those stated above with a cationic starch. Those skilled in the artof cationic polymer based retention programs will readily appreciatethat the selection of a particular polymer is furnish, filler, grade,and water quality dependent.

[0036] High molecular weight anionic flocculants which may be useful inthis invention are preferably water-soluble or dispersible vinylpolymers containing 1 mole percent or more of a monomer having ananionic charge. Accordingly, these polymers may be homopolymers or watersoluble anionically charged vinyl monomers, or copolymers of thesemonomers with for instance non-ionic monomers such as acrylamide ormethacrylamide. Examples of suitable anionic monomers include acrylicacid, methacrylamide 2-acrylamido-2-methylpropane sulfonate (AMPS) andmixture thereof as well as their corresponding water soluble ordispersible alkali metal and ammonium salts. The anionic high molecularweight polymers useful in this invention may also be either hydrolyzedacrylamide polymers or copolymers of acrylamide or its homologues, suchas methacrylamide, with acrylic acid or its homologues, such asmethacrylic acid, or with polymers of such vinyl monomers as maleicacid, itaconic acid, vinyl sulfonic acid, or other sulfonate containingmonomers. Anionic polymers may contain sulfonate or phosphonatefunctional groups or mixtures thereof, and may be prepared byderivatizing polyacrylamide or polymethacrylamide polymers orcopolymers. The most preferred high molecular weight anionic flocculantsare acrylic acid/acrylamide copolymers, and sulfonate containingpolymers such as those prepared by the polymerization of such monomersas 2-acrylamide-2-methylpropane sulfonate, acrylamido methane sulfonate,acrylamido ethane sulfonate and 2-hydroxy-3-acrylamide propane sulfonatewith acrylamide or other non-ionic vinyl monomer. When used herein thepolymers and copolymers of the anionic vinyl monomer may contain aslittle as 1 mole percent of the anionically charged monomer, andpreferably at least 10 mole percent of the anionic monomer. Again thechoice of the use of a particular anionic polymer will be dependent uponfurnish, filler, water quality, paper grade, and the like.

[0037] While most microparticle programs perform well with only a highmolecular weight cationic flocculant, we have seen surprising effectsusing the borosilicate particles of the invention with high molecularweight anionic water soluble flocculants with the addition of a cationiccoagulant.

[0038] Nonionic flocculants useful in this invention may be selectedfrom the group consisting of polyethylene oxide andpoly(meth)acrylamide. In addition to the above, it may be advantageousto utilize so called amphoteric water soluble polymers in certain cases.These polymers carry both a cationic and an anionic charge in the samepolymer chain.

[0039] The nonionic, cationic and anionic vinyl polymer flocculantsuseful herein will generally have a molecular weight of at least 500,000daltons, and preferably molecular weights of 1,000,000 daltons andhigher. Water soluble and/or dispersible flocculants useful herein mayhave a molecular weight of 5,000,000, or higher, for instance in therange of from 10 to 30 million or higher. The polymers of the inventionmay be entirely water soluble when applied to the system, or may beslightly branched (two-dimensional) or slightly cross linked (threedimensional) so long as the polymers are dispersible in water. The useof polymers which are entirely water soluble are preferred, butdispersible polymers, such as those described in WO 97/16598, may beemployed. Polymers useful may be substantially linear as such term isdefined in Langley et. al., U.S. Pat. No. 4,753,710. The upper limit formolecular weight is governed by the solubility or dispersiblity of theresulting product in the papermaking furnish.

[0040] Cationic or amphoteric starches useful in the application of thisinvention are generally described in U.S. Pat. No. 4,385,961, thedisclosure of which has been incorporated by reference into thisspecification. Cationic starch materials are generally selected from thegroup consisting of naturally occurring polymers based on carbohydratessuch as guar gum and starch. The cationic starch materials believed tobe most useful in the practice of this invention include starchmaterials derived from wheat, potato and rice. These materials may inturn be reacted to substitute ammonium groups onto the starch backbone,or cationize in accordance with the process suggested by Dondeyne et al.in WO 96/30591. In general starches useful in this invention have adegree of substitution (d.s.) of ammonium groups within the starchmolecule between about 0.01 and 0.05. The d.s. is obtained by reactingthe base starch with either 3-chloro-2-hydroxypropyl-trimethylammoniumchloride or 2,3-epoxypropyl-trimethylammonium chloride to obtain thecationized starch. As will be appreciated it is beyond the scope andintent of this invention to describe means for the cationizing of starchmaterials and these modified starch materials are well known and arereadily available from a variety of commercial sources.

[0041] Various characteristics of the cellulosic furnish, such as pH,hardness, ionic strength and cationic demand, may affect the performanceof a flocculant in a given application. The choice of flocculantinvolves consideration of the type of charge, charge density, molecularweight and type of monomers and is particularly dependent upon the waterchemistry of the furnish being treated.

[0042] Other additives may be charged to the cellulosic furnish withoutany substantial interference with the activity of the present invention.Such other additives include for instance sizing agents, such as alumand rosin, pitch control agents, extenders, biocides and the like. Thecellulosic furnish to which the retention aid program of the inventionis added may also contain pigments and or fillers such as titaniumdioxide, precipitated and/or ground calcium carbonate, or other mineralor organic fillers. It may be possible, and it is within the spirit ofthe invention that the instant invention may be combined with other socalled microparticle programs such as bentonite, kaolin, and silicasols. However data demonstrated herein shows that the particles of thesubject invention outperform these materials, and the combinationthereof may yield a performance level less than either of the materialsby themselves. Nevertheless, when papermakers change grades or furnishesit is possible that in certain situations the combination of theborosilicate materials of the invention with other microparticles may bepractical and desirable.

[0043] The borosilicate microparticles of the invention may also be usedin combination with a coagulant according to the teachings of Sofia et.al., U.S. Pat. No. 4,795,531, the disclosure of which is hereinafterincorporated by reference into this specification. Sofia teaches amicroparticle program in which a microparticle is utilized in thepresence of a cationic coagulant and a high molecular weight chargedflocculant.

[0044] The cationic coagulant materials which may find use in thisaspect of the invention include well known commercially available low-tomid molecular weight water soluble polyalkylenepolyamines includingthose prepared by the reaction of an alkylene polyamine with adifunctional alkyl halide. Materials of this type include condensationpolymers prepared from the reaction of ethylenedichloride and ammoniaethylene dichloride, ammonia and a secondary amine such as dimethylamine, epichlorohydrin-dimethylamine,epichlorohydrin-dimethylamine-ammonia, polyethyleneimines, and the like.Also useful will be low molecular weight solution polymers andcopolymers of vinyl monomers such as diallyldimethylammonium halides,especially diallyldimethylammonium chloride, dialkylaminoalkylacrylates,dialkylaminoalkylacrylate quaternaries, and the like where ‘alkyl’ ismeant to designate a group having 1-4, and preferably 1-2 carbon atoms.Preferably ‘alkyl’ is methyl. These monomers are exemplified by suchmaterials as dimethylaminoethyl acrylate, dimethyl-aminoethylmethacrylate and their water-soluble quaternary ammonium salts. Incertain cases cationic starch may be employed as the coagulant.Inorganic coagulants, e.g., alum and polyaluminum chloride, may also beused in this invention. The usage rate of inorganic coagulants istypically from 0.05 to 2 weight percent based on the dry weight of fiberin the furnish. The use of a coagulant with the borosilicatemicroparticles of this invention is optional.

[0045] The present method is applicable to all grades and types of paperproducts that contain the fillers described herein, and furtherapplicable for use on all types of pulps including, without limitation,chemical pulps, including sulfate and sulfite pulps from both hardwoodand softwood, thermo-mechanical pulps, mechanical pulps and groundwoodpulps.

[0046] The amount of any mineral filler used in the papermaking process,generally employed in a papermaking stock is from about 10 to about 30parts by weight of the filler per hundred parts by weight of dry fiberin the furnish, but the amount of such filler may at times be as low asabout 5, or even 0, parts by weight, and as high as about 40 or even 50parts by weight, same basis.

[0047] The following examples are presented to describe preferredembodiments and utilities of the invention and are not meant to limitthe invention unless otherwise stated in the claims appended hereto.

EXAMPLE 1-23

[0048] Each of the Examples shown in Table I below was prepared usingthe following general procedure and varying the relative amounts ofreagents.

[0049] Silicic acid was prepared following the general teaching ofBechtold et al., U.S. Pat. No. 2,574,902. A commercially availablesodium silicate available from OxyChem, Dallas. Tex. having a silicondioxide content of about 29% by weight and a sodium oxide content ofabout 9% by weight was diluted with deionized water to a silicon dioxideconcentration of 8-9% by weight. A cationic exchange resin such as DowexHGR-W2H or Monosphere 650C, both available from Dow Chemical Company,Midland, Mich. was regenerated to the H-form via treatment with mineralacid following well established procedures. The resin was rinsedfollowing regeneration with deionized water to insure complete removalof excess regenerant. The dilute silicate solution was then passedthrough a column of the regenerated washed resin. The resultant silicicacid was collected.

[0050] Simultaneously, an appropriate amount of borax solution (reagentgrade sodium tetraborate decahydrate) was combined with an appropriateamount of aqueous sodium hydroxide to form a “heel” for the reaction.Optionally, water may be added to the heel to insure adequate volumeduring the early stages of formation.

[0051] Freshly prepared silicic acid was then added to the “heel” withagitation at room temperature. Agitation was continued for 60 minutesafter complete addition of the silicic acid. The resulting colloidalborosilicate may be used immediately, or stored for later use. The tablebelow gives amounts of silicic acid, sodium hydroxide, and sodiumtetraborate decahydrate (borax) as well as pH. TABLE I ColloidalBorosilicates Amts Used Molar Ratio Final Example Borax NaOH Acid SolB/Si Na/Si pH  1 0.025 M(50 mL) 0.1 M(18.3 mL) 130 mL of 0.042 0.037 8.51.032 g/mL  2 0.025 M(50 mL) 0.1 M(18.5 mL) 140 mL of 0.028 0.025 8.01.046 g/mL  3 0.025 M(50 mL) 0.1 M(18.5 mL) 140 mL of 0.039 0.034 8.01.032 g/mL  4 0.025 M(50 mL) 0.1 M(22.7 g) 140 mL of 0.028 0.027 8.51.045 g/mL  5 0.025 M(50 mL) 0.1 M(24.3 g) 140 mL of 0.029 0.029 9.41.043 g/mL  6 0.1 M(50 mL) 1.0 M(9.7 mL) 140 mL of 0.117 0.116 9.4 1.043g/mL  7 0.1 M(50 mL) 1.0 M(9.7 mL) 140 mL of 0.109 0.107 9.2 1.046 g/mL 8 0.1 M(27.6 mL) 1.0 M(10.9 mL) 140 mL of 0.063 0.062 8.7 1.046 g/mL  9— — 249 g of 0    0.208 — 1.047 g/mL 10 0.1 M(50 mL) 1.0 M(9.7 g) 70 mLof 0.223 0.220 9.5 1.045 g/mL 11 0.1 M(50 mL) 1.0 M(9.7 g) 70 mL of0.223 0.220 9.5 1.045 g/mL 12 0.1 M(50 mL) 1.0 M(9.7 g) 105 mL of 0.1490.146 9.2 1.045 g/mL 13 0.1 M(446 mL) 4.57 mL of 50 wt % 1343 mL of0.117 0.115 9.1 NaOH 1.040 g/mL 14 0.1 M(223 mL) 2.39 mL of 50 wt % 1307mL of 0.063 0.062 8.5 NaOH 1.040 g/mL 15 0.1 M(50 mL) 1.0 M(24.3 mL) 150mL of 0.117 0.201 9.9 1.040 g/mL 16 0.1 M(100 mL) 2.0 mL of 50 wt % 100mL of 0.352 0.510 10.6  NaOH 1.040 g/mL 17 0.1 M(100 mL) 2.0 mL of 50 wt% 50 mL of 0.704 1.02  11.1  NaOH 1.040 g/mL 18 0.1 M(17 mL) 2.0 mL of50 wt % 150 mL of 0.039 0.242 11.0  NaOH 1.040 g/mL 19 0.1 M(50 mL) 2.0mL of 50 wt % 150 mL of 0.117 0.281 10.7  NaOH 1.040 g/mL 20 0.1 M(500mL) 12.81 mL of 1500 mL of 0.117 0.202 10.1  50 wt % NaOH 1.040 g/mL 210.1 M(500 mL) 12.81 mL of 1500 mL of 0.117 0.202 10.1  50 wt % NaOH1.040 g/mL 22 0.1 M(50 mL) 1.0 M(24.3 mL) 150 mL of 0.117 0.201 10.1 1.040 g/mL 23 0.1 M(50 mL) 1.0 M(9.7 g) 150 mL of 0.117 0.116 8.9 1.040g/mL

[0052] The commercially available compounds defined in Table II beloware used throughout the following Examples. Unless otherwise indicated,all are available from Nalco Chemical Company, One Nalco Center,Naperville Ill. 60563-1198. TABLE II Product Description Nalco ® 8671 Acommercially available colloidal silica. This material has an averageparticle size of 4 nm, a surface area of 750 m²/g, and about 15% byweight SiO₂ Nalco ® 74907 A commercially available colloidal Silicahaving an average particle size of 7 nm, a surface area of 372 m²/g, andcontaining about 15% by weight as SiO₂ Polymer “A” A commerciallyavailable copolymer having a molecular weight greater than 1 milliondaltons containing approximately 10 mole percent ofdimethylaminoethylacrylate, methyl chloride quaternary and 90 molepercent acrylamide copolymer containing approximately 26 percent byweight solids. Solvitose N A cationized potato starch which is coldwater soluble. Polymer “B” A commercially available cationic copolymerflocculant having a molecular weight greater than 1 million daltonscontaining approximately 10 mole percent copolymer ofdimethylaminoethylacrylate benzyl chloride quatemary and 90 mole percentacrylamide copolymer. Polymer “C” A commercially availableepichlorohydrin-dimethylamine condensation polymer containing about 45weight percent polymer. Polymer “G” A commercially available highmolecular weight copolymer containing approximately 10 mole percentdimethylaminoethylmethacrylate and 90 mole percent acrylamide. Polymer“D” A commercially available copolymer having a molecular weight greaterthan 1 million daltons containing approximately 30 mole percent sodiumacrylate and 70 mole percent acrylamide. Polymer “E” A commerciallyavailable copolymer flocculant having a molecular weight greater than 1million daltons containing approximately 17 mole percentdimethylaminoethyl acrylate and 83 mole percent acrylamide. Polymer “F”A commercially available copolymer flocculant having a molecular weightgreater than 1 million daltons containing approximately 10 mole percentof dimethylaminoethylacylate-methylchloride quaternary and 90 molepercent acrylamide. BMA 0 a colloidal silica sol available from EkaNobel, Surte, Sweden BMA 670 colloidal silica sol available from EkaNobel, Surte, Sweden BMA 780 colloidal aluminum coated silica solavailable from Eka Nobel, Surte, Sweden

[0053] The following describes the preparation of Example 9 appearing inTable I. A control was prepared for comparison purposes. This amounts tocarrying out the synthesis without borax in the heel. A colloidal silicawas prepared by taking 9.68 g of a commercially available sodiumsilicate and diluting with 22 g of water. The mixture was agitated witha magnetic stir bar and brought to room temperature, i.e., 25° C. Whereupon, silicic acid, 249 g with a specific gravity of 1.047, was addedover a 40 minute period. Once all of the silicic acid was added to thereaction mixture, agitation continued for an additional hour. Thecolloidal silica formed contained 8.26% by weight SiO₂. TABLE IIIProperty Comparisons Sample Id. S.A. (m²/g) S-Value DLS Dia. (nm) 8671700 63.5 12.6 BMA 0 65.7 BMA 670 489 32.6 15.4 BMA 780 435 21.6 145Example 13 1210  24.2 56.2 Example 8 1052  37.1 61.1 ACS4^(a) 619 98 4.5ACS5^(a) 545 47 13 ACS6^(a) 500 31 17 Sample 1^(b) 50 4.6 Sample 2^(b)37 13.3 Sample 3^(b) 31 16.5 Example 20 35.6 58.5

[0054] Definition: S.A.=Surface Area as determined via method describedbelow.

[0055] DLS=Dynamic Light Scattering is a method used to determineaverage particle size described below.

EXAMPLE 24

[0056] Blend of colloidal silica sol and borax

[0057] A “simple blend” control was prepared by mixing a commerciallyavailable colloidal silica and borax. A mixture was prepared at roomtemperature consisting of 50 g of 0.1 M borax solution, 92.3 g of water,and 82 g of Nalco 8671. The pH of the solution was adjusted withconcentrated hydrochloric acid to 9.5. The boron to silicon molar ratiowas 0.098, while sodium to silicon molar ratio was 0.049.

EXAMPLE 25

[0058] Ex. 3 of U.S. Pat. No. 4,954,220

[0059] An anionic polysilicate microgel, as described in U.S. Pat. No.4,954,220 by Rushmere. Example 3 was tested. The purpose of the examplewithin the subject patent was to demonstrate that certain ionic saltsinduce the formation of polysilicic acid microgel. These salts arechosen so as to adjust the pH of a sodium silicate solution into theunstable, pH range. A 5% by weight borax solution was prepared from 5 gof sodium orthoborate•decahydrate and 95 g of water. A 3.75% sodiumsilicate solution was prepared from 12.5 g of a commercially availablesodium silicate, containing 29.3% as silicon dioxide and 9.0% as sodiumoxide, and 87.5 g of water. Following the instructions of the subjectpatent, 60 g of the 5% borax solution was mixed with 40 g of the dilutesodium silicate solution. The mixture was allowed to stand for 8 minutesafter which time it was further diluted to 0.125 weight % as silicondioxide. It was confirmed repeatedly in our laboratory, that the 1.5%silicon dioxide solution of polysilicic acid microgel gelled uponstanding at 23 minutes. The boron to silicon molar ratio was 1.24.Similarly, the sodium to silicon molar ratio was 1.2. The final productsolids were 0.125% by weight actives.

EXAMPLE 26

[0060] Borax Solution

[0061] A blank devoid of silica was prepared for study using 100 mL of0.1 M Borax solution, 48.6 mL of 1 M NaOH solution and 300 mL of water.The solution pH was 13.

[0062] The following test protocols were used in conducting theexperiments presented below.

Preparation of Synthetic Standard Furnishes

[0063] Alkaline Furnish—The alkaline furnish has a pH of 8.1 and iscomposed of 70 weight percent cellulosic fiber and 30% weight percentfiller diluted to an overall consistency of 0.5% by weight usingsynthetic formulation water. The cellulosic fiber consists of 60% byweight bleached hardwood kraft and 40% by weight bleached softwoodkraft. These are prepared from dry lap beaten separately to a CanadianStandard Freeness (CSF) value ranging from 340 to 380 CSF. The fillerwas a commercial ground calcium carbonate provided in dry form. Theformulation water contained 200 ppm calcium hardness (added as CaCl₂),152 ppm magnesium hardness (added as MgSO₄), and 110 ppm bicarbonatealkalinity (added as NaHCO₃)

[0064] Acid Furnish—The acid furnish consisted of the same bleachedkraft hardwood/softwood weight ratio. i.e., 60/40. The total solids ofthe furnish comprised 92.5% by weight cellulosic fiber and 7.5% byweight filler. The filler was a combination of 2.5% by weight titaniumdioxide and 5.0 percent by weight kaolin clay. Other additives includedalum dosed at 20 lbs active per ton dry solids. The pH of the furnishwas adjusted with 50% sulfuric acid such that the furnish pH was 4.8after alum addition.

Britt Jar Test

[0065] The Britt Jar Test used a Britt CF Dynamic Drainage Jar developedby K. W. Britt of New York University, which generally consists of anupper chamber of about 1 liter capacity and a bottom drainage chamber,the chambers being separated by a support screen and a drainage screen.Below the drainage chamber is a flexible tube extending downwardequipped with a clamp for closure. The upper chamber is provided with a2-inch, 3-blade propeller to create controlled shear conditions in theupper chamber. The test was done following the sequence below: TABLE IVAlkaline Furnish Test Protocol Agitator Time Speed (seconds) (rpm)Action  0 750 Commence shear via mixing-Add cationic starch. 10 1500 Add Flocculant. 40 750 Reduce the shear via mixing speed. 50 750 Add themicroparticle. 60 750 Open the tube clamp to commence drainage. 90 750Stop draining.

[0066] TABLE V Acid Furnish Test Protocol Time Agitator Speed (seconds)(rpm) Action  0 750 Commence shear via mixing. Add cationic starch andalum. 10 1500  Add Flocculant. 40 750 Reduce the shear via mixing speed.50 750 Add the microparticle. 60 750 Open the tube clamp to commencedrainage. 90 750 Stop draining.

[0067] In all cases above, the starch used was Solvitose N, a cationicpotato starch, commercially available from Nalco. In the case of thealkaline furnish, the cationic starch was introduced at 10 lbs/ton dryweight of furnish solids or 0.50 parts by weight per hundred parts ofdry stock solids, while the flocculant was added at 6 lbs/ton dry weightof furnish solids or 0.30 parts by weight per hundred parts of dry stocksolids. In the case of the acid furnish, the additive dosages were: 20lbs/ton dry weight of furnish solids of active alum (i.e., 1.00 parts byweight per hundred parts of dry stock solids), 10 lbs/ton dry weight offurnish solids or 0.50 parts by weight per hundred parts of dry stocksolids of cationic starch, and the flocculant was added at 6 lbs/ton dryweight of furnish solids or 0.30 parts by weight per hundred parts ofdry stock solids.

[0068] The material so drained from the Britt Jar (the “filtrate”) iscollected and diluted with water to provide a turbidity which can bemeasured conveniently. The turbidity of such diluted filtrate, measuredin Nephelometric Turbidity Units or NTUs, is then determined. Theturbidity of such a filtrate is inversely proportional to thepapermaking retention performance; the lower the turbidity value, thehigher is the retention of filler and/or fines. The turbidity valueswere determined using a Hach Turbidimeter. In some cases, instead ofmeasuring turbidity, the % Transmittance (% T) of the sample wasdetermined using a DigiDisc Photometer. The transmittance is directlyproportional to papermaking retention performance; the higher thetransmittance value, the higher is the retention value.

SLM (Scanning Laser Microscopy)

[0069] The Scanning Laser Microscopy employed in the following examplesis outlined in U.S. Pat. No. 4,871,251. issued to Preikschat, F. K. andE. (1989) and generally consists of a laser source, optics to deliverthe incident light to and retrieve the scattered light from the furnish,a photodiode, and signal analysis hardware. Commercial instruments areavailable from Lasentec™, Redmond, Wash.

[0070] The experiment consists of taking 300 mL of cellulose fibercontaining slurry and placing this in the appropriate mixing beaker.Shear is provided to the furnish via a variable speed motor andpropeller. The propeller is set at a fixed distance from the probewindow to ensure slurry movement across the window. A typical dosingsequence is shown below. TABLE VI Scanning Laser Microscopy TestProtocol Time (minutes) Action 0 Commence mixing. Record baseline flocsize. 1 Add cationic starch. Record floc size change. 2 Add flocculant.Record floc size change. 4 Add the microparticle. Record floc sizechange. 7 Terminate experiment.

[0071] The change in mean chord length of the flocs present in thefurnish relates to papermaking retention performance; the greater thechange induced by the treatment, the higher the retention value.

Surface Area Measurement

[0072] Surface area reported herein is obtained by measuring theadsorption of base on the surface of sol particles. The method isdescribed by Sears in Analytical Chemistry, 28(12), 1981-1983(1956). Asindicated by Iler (“The Chemistry of Silica”, John Wiley & Sons, 1979,353), it is the “value for comparing relative surface areas of particlesizes in a given system which can be standardized.” Simply put, themethod involves the titration of surface silanol groups with a standardsolution of sodium hydroxide, of a know amount of silica(i.e., grams),in a saturated sodium chloride solution. The resulting volume of titrantis converted to surface area.

S-value Determination

[0073] Another characteristic of colloids in general, is the amount ofspace occupied by the dispersed phase. One method for determining thiswas first developed by R. Iler and R. Dalton and reported in J. Phys.Chem., 60(1956), 955-957. In colloidal silica systems, they showed thatthe S-value relates to the degree of aggregation formed within theproduct. A lower S-value indicates a greater volume is occupied by thesame weight of colloidal silica.

DLS Particle Size Measurement

[0074] Dynanic Light Scattering (DLS) or Photon Correlation Spectroscopy(PCS) has been used to measure particle size in the submicron rangesince as early as 1984. An early treatment of the subject is found in“Modern Methods of Particle Size Analysis”, H. Barth, editor, Wiley, NewYork. 1984. The method consists of filtering a small volume of thesample through a 0.45 micron membrane filter to remove straycontamination such as dust or dirt. The sample is then placed in acuvette which in turn is placed in the path of a focused laser beam. Thescattered light is collected at 90° to the incident beam and analyzed toyield the average particle size. The present work used a Coulter® N4unit, commercially available from Coulter Corporation, ScientificInstruments.

[0075] The following examples show the results of a comparison betweenthe colloidal borosilicate compositions of the invention and the priorart in several papermaking furnishes. Britt Jar Results Alkaline Furnish10 lbs/t Solvitose N followed by 6 lbs/t Polymer “A” Turbidity/3 (NTU)Turbidity Improvement (%) Compound 0.0 lb/t 0.5 lb/t 1.0 lb/t 1.5 lb/t2.0 lb/t 0.5 lb/t 1.0 lb/t 1.5 lb/t 2.0 lb/t Blank 380 8671 355 310 210205  6.6 18.4 44.7 46.1 Example 3 225 137 160 110 40.8 63.9 57.9 71.1Example 6 180 150 125 170 52.6 60.5 67.1 55.3 Example 7 170 145 180 18055.3 61.8 52.6 52.6 Blank 350 8671 316 340 210 180  9.7  2.9 40.0 48.6Example 8 205 170 140 130 41.4 51.4 60.0 62.9 20 lbs/t Alum, 10 lbs/tSolvitose N followed by 6 lbs/t Polymer “A” Turbidity/3 (NTU) TurbidityImprovement (%) Compound 0.0 lb/t 0.5 lb/t 1.0 lb/t 2.0 lb/t 3.0 lb/t4.0 lb/t 0.5 lb/t 1.0 lb/t 2.0 lb/t 3.0 lb/t 4.0 lb/t Blank 390 8671 330355 290 270 230 15.4  9.0 25.6 30.8 41.0 Example 6 260 180 155 130 33.353.8 60.3 66.7 Turbidity/3 (NTU) Turbidity Improvement (%) Compound 0.0lb/t 0.5 lb/t 1.0 lb/t 1.5 lb/t 2.0 lb/t 0.5 lb/t 1.0 lb/t 1.5 lb/t 2.0lb/t Blank 318 8671 270 288 255 250 15.1 9.4 19.8 21.4 Example 25 - Ex.3 298 255 235 220 6.3 19.8 26.1 30.8 of U.S. Pat. No. 4,954.220 Example13 250 225 180 160 21.4 29.2 43.4 49.7 Blank 360 8671 300 313 275 29516.7 13.1 23.6 18.1 Example 6 270 225 180 150 25.0 37.5 50.0 58.3Example 7 260 210 180 195 27.8 41.7 50.0 45.8 Example 8 310 280 210 15513.9 22.2 41.7 56.9 Blank 345 8671 245 235 220 230 29.0 31.9 36.2 33.3Example 13 220 213 195 155 36.2 38.3 43.5 55.1 Example 6 250 200 195 13027.5 42.0 43.5 62.3 Example 14 250 228 205 170 27.5 33.9 40.6 50.7Example 8 270 250 210 200 21.7 27.5 39.1 42.0 5Bentonite 290 250 210 20515.9 27.5 39.1 40.6 Turbidity/3 (NTU) Turbidity Improvement (%) Compound0.0 lb/t 2.0 lb/t 2.0 lb/t Blank 345 Example 26 [Borax(only)] 345  0.0Example 26 [Borax @ 180X (only)] 280 18.8 8671 275 20.3 Example 24 [8671with Borax] 280 18.8 Example 6 115 66.7 Example 14 170 50.7 Example 13155 55.1

[0076] SLM Data Delta @ Maximum Improvement (microns) @ (%) @ CompoundDescription 2.0 lb/t 2.0 lb/t Acid Furnish 10 lbs/t Alum, 10 lbs/tSolvitose N followed by 4 lbs/t Polymer “A” 8671 colloidal silica 3.65Example 13 35.3 867 Example 24 8671 + borax 2.4 −34 (aged 2 hrs)Alkaline Furnish 10 lbs/t Solvitose N followed by 6 lbs/t Polymer “A”8671 colloidal silica 23.4 8671 colloidal silica 18.7 8671 colloidalsilica 19.8 mean 20.6 standard deviation 2.5 Example 24 8671 + borax23.1 12 Example 13 57.9 181

EXAMPLE 27

[0077] The following work was done on a commercial alkaline fine papercomposed of 100% bleached hardwood virgin fibers. Ash content was 8% viaprecipitated calcium carbonate: Consistency was targeted at 1%. Thefurnish also contained recycled coated broke. SLM Data CommercialAlkaline Fine Paper 20 lbs/t Cationic Starch followed by 2 lbs/t Polymer“B” Delta @ Maximum Improvement (microns) (%) Compound Description @2.0lb/t @2.0 lb/t 8671 colloidal silica 5.17 Example 6 13.5 161 SLM DataAlkaline Furnish 10 lbs/t Solvitose N followed by 6 lbs/t Polymer “A”Delta @ maximum (microns) Improvement (%) Compound 0.5 lb/t 1.0 lb/t 2.0lb/t 0.5 lb/t 1.0 lb/t 2.0 lb/t 8671  9.5 18.8 27.0 Example 7 35.9 50.374.4 277.9 167.6 175.6 Example 6 28.4 57.7 74.1 198.9 206.9 174.4

[0078] SLM Data Alkaline Furnish 10 lbs/t Solvitose N followed by 6lbs/t Polymer “A” Delta @ maximum (microns) Improvement (%) Compound 0.5lb/t 1.0 lb/t 1.5 lb/t 2.0 lb/t 0.5 lb/t 1.0 lb/t 1.5 lb/t 2.0 lb/t 86717.0 13.1 24.6 Example 3 29.2 42.6 66.9 317.1 225.2 172.0

EXAMPLE 28

[0079] The following data were collected using an alkaline furnishprepared using European hardwood and softwood drylap. The preparationfollows that outlined above for “standard” alkaline furnish. Thealkaline furnish has a pH of 8.1 and is composed of 70 weight percentcellulosic fiber and 30% weight percent filler diluted to an overallconsistency of 0.5% by weight using synthetic formulation water. Thecellulosic fiber consists of 60% by weight European bleached hardwoodkraft and 40% by weight European bleached softwood kraft. These areprepared from dry lap beaten separately to a Canadian Standard Freenessvalue ranging from 340 to 380 CSF. The filler was a commercial groundcalcium carbonate provided in dry form. The formulation water contained200 ppm calcium hardness (added as CaCl₂), 152 ppm magnesium hardness(added as MgSO₄) and 110 ppm bicarbonate alkalinity (added as NaHCO₃).Britt Jar Results European Alkaline Furnish 10 lbs/t Solvitose Nfollowed by 6 lbs/t Polymer “A” Turbidity/3 (NTU) Improvement (%)Compound 0.0 lb/t 0.5 lb/t 1.0 lb/t 2.0 lb/t 0.5 lb/t 1.0 lb/t 2.0 lb/tBlank 465 8671 404 255 104 13.1 45.2 77.6 N-74907 434 360 263 6.7 22.643.4 Example 13 236 80 60 49.2 82.8 87.1

[0080] Britt Jar Results European Alkaline Furnish 10 lbs/t Solvitose Nfollowed by 6 lbs/t Polymer “A” Turbidity Turbidity/3 Improvement (NTU)(%) Compound 0.0 lb/t 1.0 lb/t 1.0 lb/t Blank 465 8671 255 45.2 N-74907360 22.6 Example 13 84.0 81.9 Example 15 33.0 92.9 SLM Data EuropeanAlkaline Furnish 10 lbs/t Solvitose N followed by 6 lbs/t Polymer “A”Delta Improvement @ Maximum (%) Compound Description @2.0 lb/t @2.0 lb/t8671 colloidal silica 16.6 N-74907 colloidal silica  5.3 −68 BentoniteNatural Mineral 54.4 228 Example 13 Subject of patent 45.5 174

EXAMPLE 29

[0081] The next furnish, a commercial European furnish, is used toprepare coated alkaline fine paper. The furnish consists of 50%cellulosic fiber, i.e. 100% bleached kraft fiber, and 50% filler. Thefiller is ground calcium carbonate. The furnish has a pH of 7.4 and anoverall consistency of 1.5%. The Britt Jar and SLM testing protocolconsisted of the following sequence: Commercial European AlkalineFurnish Test Protocol Agitator Time Speed (seconds) (rpm) Action  0 800Commence shear via mixing.  5 800 Add Coagulant (Polymer “C” @ 0.5kg/t). 15 800 Add Alkyl Ketene Dimer Size @ 3 kg/t. 20 800 AddFlocculant A (Polymer “G” @ 0.35 kg/t). 30 800 Add Flocculant B (Polymer“D” @ 0.35 kg/t). 35 800 Add Microparticle @ 0.5 kg/t. 40 800 Open thetube clamp to commence drainage. 45 800 Begin collecting sample forTurbidity. 75 800 Stop draining.

[0082] Britt Jar Results Commercial European Alkaline Furnish SeeSequence Above. Turbidity Turbidity/3 Improvement (NTU) (%) Compound 0.0lb/t 0.5 kg/t 0.5 kg/t Blank 753 8671 533 29.2 Bentonite 363 51.8Example 13 393 47.8 Example 15 362 51.9 SLM Data Commercial EuropeanAlkaline Furnish See Sequence Above. Delta @ Maximum Improvement(microns) (%) Compound Description @2.0 kg/t @2.0 kg/t 8671 colloidalsilica  6.6 N-74907 colloidal silica  4.4 −33 Bentonite Natural Mineral26.0 294 Example 13 Subject of patent 25.1 280 Example 15 Subject ofpatent 29.8 352

EXAMPLE 30

[0083] The next furnish, a commercial European furnish, is an acidfurnish composed of 40% TMP fiber consisting of sulfite bleached andunbleached, 40% is kraft fiber and the remaining is coated broke. Thefiller is kaolin clay. The final product is a LWC(i.e., Light WeightCoated) grade. In particular, the furnish pH was 4.8, with a consistencyof 0.71%. The Britt Jar and SLM testing protocol consisted of thefollowing sequence: Commercial European Acid TMP Furnish Test ProtocolTime Agitator Speed (seconds) (rpm) Action  0 800 Commence shear viamixing. 10 800 Add 8 kg/t of alum and 5 kg/Cationic Starch. 15 800 AddCoagulant Polymer “C”@5 kg/t). 30 800 Add Flocculant (Polymer “E”@0.66kg/t). 35 800 Add Microparticle @2.0 kg/t. 40 800 Open the tube clamp tocommence drainage. 45 800 Begin collecting sample for Turbidity. 75 800Stop draining. Britt Jar Results Commercial European Acid TMP FurnishSee Sequence Above. Turbidity Turbidity/3 Improvement (NTU) (%) Compound0.01 b/t 2.0 kg/t 2.0 kg/t Blank 348 8671 335 3.7 N-74907 360 −3.4Bentonite 227 34.8 Example 13 233 33.0 Example 15 247 29.0 SLM DataCommercial European Acid TMP Furnish See Sequence Above. Delta @ MaximumImprovement (microns) (%) Compound Description @2.0 kg/t @2.0 kg/t 8671colloidal silica −0.3 N-74907 colloidal silica 3.4 1233 BentoniteNatural Mineral 21.1 7133 Example 13 Subject of patent 10.7 3667 Example15 Subject of patent 10.0 3433

[0084] Sequence the same, however the dosages of polymers changed. Alumwas added at 6.7 kg/t, cationic starch added at 5.0 kg/t, the coagulantwas added at 5.0 kg/t, the flocculant was added at 0.66 kg/t just priorto the microparticle being added at 2.0 kg/t.

EXAMPLE 31

[0085] The next furnish, a commercial European furnish, is an alkalinefurnish. The alkaline furnish consists of 32% Kraft fiber, 48% broke,and 20% ash. The Kraft fiber consists of 63% hardwood and 37% softwoodkraft pulp. The 20% ash is composed of equal components of precipitatedand ground calcium carbonate. The furnish pH was 8.25, with aconsistency of 1.2%. The SLM testing protocol consisted of the followingsequence: at 30 seconds the coagulant, Polymer “C”, was added at 1.0kg/t; this was followed 30 seconds later with the flocculant, Polymer“F” at 0.5 kg/t; and the last additive was the microparticle at 90seconds and at 1.0 kg/t. SLM Data Commercial European Alkaline FurnishSee Sequence Above. Compound Description @1.0 kg/t @1.0 kg/t 8671colloidal silica 19.8 N-74907 colloidal silica 31.3 58 Bentonite NaturalMineral 26.0 31 Example 13 Subject of patent 36.1 82 Example 15 Subjectof patent 42.1 113 

EXAMPLE 32

[0086] The next furnish, a commercial European furnish, is used to makea neutral coated wood-containing sheet. The furnish consisted of CTMP,coated broke and some Kraft pulp. The furnish pH was 7.5, with aconsistency of 0.7%. Of this some 20% was ash. The SLM testing protocolconsisted of the following sequence: beginning with cationic starch at 8kg/t; at 60 seconds the coagulant, Polymer “C”, was added at 4.8 kg/t;this was followed 30 seconds later with the flocculant, Polymer “E” at0.9 kg/t; and the last additive was the microparticle at 120 seconds andat 2.0 kg/t. SLM Data Commercial European CTMP Furnish See SequenceAbove. Delta @ Maximum Improvement (microns) (%) Compound Description@1.0 kg/t @1.0 kg/t 8671 colloidal silica 8.98 N-74907 colloidal silica3.37 −62 Example 13 Subject of patent 18.9 110 Example 15 Subject ofpatent 27.3 204

[0087] Changes can be made in the composition, operation and arrangementof the method of the present invention described herein withoutdeparting from the concept and scope of the invention as defined in thefollowing claims:

1. A synthetic borosilicate having a particle size of from 1 to 2000 nmand a surface area of from 15 to 3000 m²/g.
 2. The syntheticborosilicate of claim 1 wherein the particle size is from 1 to 200 nm.3. The synthetic borosilicate of claim 1 wherein the particle size isfrom 20 to 80 nm.
 4. The synthetic borosilicate of claim 1 having asurface area of from 250 to 3000 m²/g.
 5. The synthetic borosilicate ofclaim 1 having a surface area of from 700 to 3000 m²/g.
 6. A syntheticborosilicate composition having: a. a mole ratio of boron to silicon offrom about 1:1000 to about 100:1; b. a mole ratio of alkali metal tosilicon of from about 6:1000 to about 1.04:1; c. a particle size of fromabout 1 to 2000 nm; and, d. a surface area of from about 15 to 3000m²/g.
 7. The composition of claim 6 wherein: a. the mole ratio of boronto silicon is from about 1:100 to 2:5; b. the mole ratio of alkali metalto silicon is from about 6:1000 to 1.04:1; c. the particle size is fromabout 1 nm to about 80 nm; and, d. the surface area is from about 250to3000 m²/g.
 8. The composition of claim 6 herein: a. the mole ratio ofboron to silicon is from about 1:100 to 2:5; b. the mole ratio of alkalimetal to silicon is from about 6:1000 to 1.04:1; c. the particle size isfrom about 20-80 nm; and, d. the surface area is from about 700 to 3000m²/g.
 9. A colloidal borosilicate having: a. a mole ratio of boron tosilicon of from about 1:1000 to about 100:1; b. a mole ratio of alkalimetal to silicon of from about 6:1000 to about 1.04:1; c. a particlesize of from about 1 nm to about 2000 nm; and, d. a surface area of fromabout 15-3000 m²/g, said borosilicate having been prepared by the stepsof: a. admixing a dilute aqueous solution of silicic acid with a diluteaqueous solution of an alkali metal borate; and then, b. recovering anaqueous suspension of a colloidal borosilicate having a pH of 6-14. 10.The colloidal borosilicate of claim 9 wherein said borosilicate has thefollowing properties: a. a mole ratio of boron to silicon is from about1:100 to 2:5; b. a mole ratio of alkali metal to silicon is from about6:1000 to 1.04:1; c. a particle size is from about 1 nm to about 200 nm;and, d. a surface area is from about 250-3000 m²/g.
 11. The colloidalborosilicate of claim 9 wherein said borosilicate has the followingproperties: a. a mole ratio of boron to silicon is from about 1:100 to2:5; b. a mole ratio of alkali metal to silicon is from about 6:1000 to1.04:1; c. a particle size is from about 20-80 nm; and, d. a surfacearea is from about 700 to 3000 m²/g.
 12. The colloidal borosilicate ofclaim 9 wherein the dilute aqueous solution of silicic acid is added tothe dilute aqueous solution of the alkali metal borate.
 13. Thecolloidal borosilicate of claim 10 wherein the dilute aqueous solutionof silicic acid is added to the dilute aqueous solution of the alkalimetal borate.
 14. The colloidal borosilicate of claim 11 wherein thedilute aqueous solution of silicic acid is added to the dilute aqueoussolution of alkali metal borate.
 15. A method for the preparation of acolloidal borosilicate which comprises the steps of: a. contacting adilute aqueous solution of an alkali metal silicate with a cationexchange resin to produce a silicic acid; b. forming a heel by mixingtogether a dilute aqueous solution of an alkali metal borate with analkali metal hydroxide to form an aqueous solution containing 0.01 to 30percent B₂O₃, having a pH of from 7 to 10.5, c. adding the dilutesilicic acid to the aqueous solution with agitation; and then, d.recovering an aqueous colloidal borosilicate.
 16. The borosilicateprepared by the method of claim 15 .
 17. A method for the manufacture ofa cellulosic sheet which comprises: a. forming a cellulosic furnishcontaining from 0.01 to 1.5% by weight cellulosic fiber; b. adding tothe furnish: (i) from about 0.00005 to about 1.25% by weight, based onthe dry weight of fiber in the furnish, of a borosilicate having a moleratio of boron to silicon of from about 1:1000 to about 100:1, a moleratio of alkali metal to silicon of from about 6:1000 to about 1.04:1, aparticle size of from about 1 to 2000 nm; and a surface area of fromabout 15 to 3000 m²/g.; and, (ii.) from about 0.001 to about 0.5% byweight, based on the dry weight of fiber in the furnish of asubstantially water soluble polymeric flocculant having a molecularweight greater than 500,000 daltons: and then, c. dewatering saidfurnish to obtain a cellulosic sheet.
 18. The method of claim 17 whereinthe borosilicate is a colloidal borosilicate.
 19. The method of claim 18wherein the borosilicate has: a. a mole ratio of boron to silicon isfrom about 1:100 to 2:5; b. a mole ratio of alkali metal to silicon isfrom about 6:1000 to 1.04:1; c. a particle size is from about 1 nm toabout 200 nm; and, d. a surface area is from about 250-3000 m²/g. 20.The method of claim 18 wherein the borosilicate has: a. a mole ratio ofboron to silicon is from about 1:100 to 2:5; b. a mole ratio of alkalimetal to silicon is from about 6:1000 to 1.04:1; c. a particle size isfrom about 20-80 nm: and, d. a surface area is from about 700 to 3000m²/g.
 21. The method according to claim 20 , wherein the cellulosicsheet selected from the group consisting of fine paper, board, andnewsprint.
 22. The method according to claim 20 wherein the colloidalborosilicate is added after the flocculant.
 23. The method according toclaim 20 , further comprising the additional step of adding a cationiccoagulant to the furnish before adding the flocculant to the furnish.24. The method according to claim 19 , wherein the colloidalborosilicate is added after the flocculant.
 25. The method according toclaim 20 , further comprising the addition of a material selected fromthe group consisting of bentonite, kaolin, hectorite, talc, and mixturesthereof.
 26. The method according to claim 20 , wherein the flocculantis a cationically charged flocculant selected from one or more membersof the group consisting of polymers of dimethylaminoethyl methacrylate,dimethylaminoethyl acrylate, diethylaminoethyl acrylate,diethylaminoethyl methacrylate or their quaternary ammonium salts,diallylcyclohexylamine hydrochloride, diallyldimethylammonium halide,methacrylamidopropyltrimethylammonium halide, allyl amine, and mannichreaction derivatized polyacrylamides, said polymers having a molecularweight of greater than 1,000,000 daltons or cationized starch or guargum.
 27. The method according to claim 20 , wherein the flocculant is ananionically charged flocculant selected from the group consisting ofpolymers of acrylic acid, 2-acrylamido-2-methylpropane sulfonate, maleicacid, itaconic acid, vinyl sulfonic acid and 2-hydroxy-3-acrylamidepropane sulfonate, their water soluble alkali metal salts and hydrolyzedacrylamide polymers said polymers having a molecular weight of greaterthan 1,000,000 daltons.
 28. The method according to claim 20 , whereinthe flocculant is a nonionic flocculant selected from the groupconsisting of polyethylene oxide and poly(meth)acrylamide.
 29. Themethod according to claim 20 , wherein the flocculant is added in anamount of from about 0.005 to about 0.20% by weight based on the dryweight of fiber in the furnish.
 30. The method according to claim 20 ,wherein the colloidal borosilicate is added in an amount of from about0.005 to about 0.25% by weight based on the dry weight of fiber in thefurnish.
 31. The method according to claim 18 , wherein the colloidalborosilicate is added in an amount of from about 0.005 to about 0.15%based on the dry weight of fiber in the furnish.
 32. The methodaccording to claim 20 , wherein a cationic coagulant is added as anadditional component in an amount of from about 0.005 to about 1.25% byweight based on the dry weight of fiber in the furnish.
 33. The methodaccording to claim 32 , wherein the coagulant is added in an amount offrom about 0.025 to 0.5% based on the dry weight of fiber in thefurnish.
 34. A method for increasing drainage of a papermaking furnishon a papermaking machine comprising: adding to a papermaking furnishprior to placing said furnish on a papermaking machine from about0.00005 to about 1.25% by weight of a colloidal borosilicate, based ondry weight of fiber in the furnish, and, about 0.001 to about 0.5% byweight based on dry weight of the fiber in the furnish of a polymericflocculant; placing the furnish on the papermaking machine; and then,subjecting the furnish to papermaking conditions whereby the rate ofdrainage of water from the furnish on the papermaking machine isincreased.
 35. The method according to claim 34 , wherein thepapermaking furnish is selected from the group consisting of a furnishused to prepare paper, board corrugated, test board, recycled, andnewsprint paper making furnishes.
 36. The method according to claim 34 ,wherein the colloidal borosilicate is added to the furnish after theflocculant.
 37. The method according to claim 34 , further comprisingthe additional step of adding a cationic coagulant to the furnish at apoint prior to the addition of the flocculant.
 38. The method accordingto claim 34 , wherein the colloidal borosilicate is added to the furnishafter the flocculant.
 39. The method according to claim 34 , furthercomprising the additional step of adding a composition selected from agroup consisting of: bentonite, kaolin, hectorite, talc, and mixturesthereof to the furnish.
 40. The method according to claim 34 , whereinthe flocculant is a cationic flocculant selected from the groupconsisting of polymers of dimethylaminoethyl methacrylate,dimethylaminoethyl acrylate, diethylaminoethyl acrylate,diethylaminoethyl methacrylate or their quaternary ammonium salts,diallylcyclohexylamine hydrochloride, diallyldimethylammonium halide,methacrylamidopropyltrimethylammonium halide, allyl amine, mannichreaction derivatized polyacrylamides and cationized starch, saidpolymers having a molecular weight of greater than 10,000,000 daltons.41. The method according to claim 34 , wherein the flocculant is ananionic flocculant selected from the group consisting of polymers ofacrylic acid, 2-acrylamido-2-methylpropane sulfonate, maleic acid,itaconic acid, vinyl sulfonic acid and 2-hydroxy-3-acrylamide propanesulfonate, their water soluble alkali metal salts and hydrolyzedacrylamide polymers said polymers having a molecular weight of greaterthan 10,000,000 daltons.
 42. The method according to claim 34 , whereinthe flocculant is a nonionic flocculant selected from the groupconsisting of polyethylene oxide and polyacrylamide.
 43. The methodaccording to claim 34 , wherein the flocculant has a molecular weight offrom about 500,000 to about 30,000,000 daltons.
 44. The method accordingto claim 43 , wherein the flocculant is added in an amount of from about0.005 to about 0.2% by weight based on the dry weight of fiber in thefurnish.
 45. The method according to claim 44 , wherein the colloidalborosilicate is added in an amount of from about 0.005 to about 0.25%weight based on the dry weight of fiber in the furnish.
 46. The methodaccording to claim 44 , wherein the colloidal borosilicate is added inan amount of from about 0.005 to about 0.15% by weight based on the dryweight of fiber in the furnish.
 47. The method according to claim 37 ,wherein the coagulant is added in an amount of from about 0.005 to about1.25% by weight based on the dry weight of fiber in the furnish.
 48. Themethod according to claim 47 , wherein the coagulant is added in anamount of from about 0.025 to about 0.5% by weight based on the dryweight of fiber in the furnish.
 49. A method for increasing the drainagerate of water from the solid components of a paper mill furnishcomprising: adding to the paper mill furnish from about 0.00005 to about1.25% by dry weight, based on fiber in the furnish, of a borosilicateand from about 0.005 to about 5.0% by weight, based on fiber in thefurnish, of a cationic starch; and then, flocculating the furnishwhereby the drainage rate of water from the paper mill furnish isincreased.
 50. The method according to claim 49 , wherein the paper millfurnish is selected from the group consisting of fine paper, board, andnewsprint paper mill furnishes.
 51. The method according to claim 49 ,wherein the colloidal borosilicate is added after the cationic starch.52. The method according to claim 49 , further comprising the step ofadding a cationic coagulant to the furnish before adding the cationicstarch to the furnish.
 53. The method according to claim 49 , furthercomprising the additional step of adding a composition selected from agroup consisting of bentonite, talc, and mixtures thereof to thefurnish.
 54. The method according to claim 49 , wherein the cationicstarch has a molecular weight of from about 500,000 to about 30,000,000daltons.
 55. The method according to claim 49 , wherein the cationicstarch is added in an amount of from about 0.05 to about 1.5% by weightbased on the dry weight of fiber in the furnish.
 56. The methodaccording to claim 55 , wherein the colloidal borosilicate is added inan amount of from about 0.005 to about 0.25% by weight based on the dryweight of fiber in the furnish.
 57. The method according to claim 55 ,wherein the colloidal borosilicate is added in an amount of from about0.005 to about 0.15% by dry weight based on fiber in the furnish. 58.The method according to claim 52 , wherein the coagulant is added in anamount of from about 0.005 to about 1.25% by weight based on the dryweight of fiber in the furnish.
 59. The method according to claim 58 ,wherein the coagulant is added in an amount of from about 0.025 to about0.5% by weight based on the dry weight of fiber in the furnish.
 60. Amethod for flocculating the components of a paper mill furnish in apapermaking system into a cellulosic sheet comprising: adding to apapermaking furnish from about 0.00005 to about 1.25% by weight, basedon dry weight of fiber in the furnish, of a colloidal borosilicate andabout 0.001 to about 0.5% by weight, based on dry weight of fiber in thefurnish, of a flocculant; subjecting such furnish to papermakingconditions; and recovering a cellulosic sheet.
 61. The method accordingto claim 60 , wherein the paper mill furnish is selected from the groupconsisting of fine paper, board, and newsprint paper mill furnish. 62.The method according to claim 61 , wherein the colloidal borosilicate isadded after the flocculant.
 63. The method according to claim 60 ,further comprising the addition of a composition selected from a groupconsisting of bentonite, talc, hectorite, kaolin and mixtures thereof.64. The method according to claim 60 , wherein the colloidalborosilicate is added in an amount of from about 0.005 to about 0.25% bydry weight based on fiber in the furnish.
 65. The method according toclaim 62 , wherein the colloidal borosilicate is added in an amount offrom about 0.005 to about 0.15% by dry weight based on fiber in thefurnish.
 66. The method according to claim 60 , wherein the flocculantis added in an amount of from about 0.001 to about 0.5% by weight basedon fiber in the furnish.
 67. A method for increasing retention of finesand fillers on a cellulosic sheet and improving the rate of drainage ofliquid from a cellulosic sheet formed from a papermaking furnishsubjected to papermaking conditions comprising the steps of: adding tothe papermaking furnish from about 0.00005 to about 1.25% by weight of acolloidal borosilicate based on dry weight of fiber and, from about0.001 to about 0.5% by weight of a flocculant based on dry weight offiber in the furnish, and then subjecting the furnish to papermakingconditions and recovering a cellulosic sheet, whereby the retention offines and fillers and on said sheet and the rate of drainage of liquidfrom said sheet is increased.
 68. The method according to claim 67 ,wherein the paper-making furnish is selected from the group consistingof fine paper, board, and newsprint paper making furnishes.
 69. Themethod according to claim 67 , wherein the colloidal borosilicate isadded after the flocculant.
 70. The method according to claim 67 ,further comprising the addition of a composition selected from a groupconsisting of: bentonite, talc, hectorite, kaolin and mixtures thereof.71. The method according to claim 67 , wherein the colloidalborosilicate is added in an amount of from about 0.00005 to about 1.25%by weight based on the dry weight of fiber in the furnish.
 72. Themethod according to claim 67 , wherein the colloidal borosilicate isadded in an amount of from about 0.005 to about 0.15% by weight based ondry weight of fiber in the furnish.
 73. The method according to claim 67, wherein the flocculant is added in an amount of from about 0.001 toabout 0.5% by weight based on dry weight of fiber in the furnish. 74.The method of claim 69 wherein the furnish is subjected to a shear stageafter the addition of flocculant but prior to the addition ofborosilicate.